CN101085764A - Synthesis method for (methyl)glycidyl acrylate - Google Patents
Synthesis method for (methyl)glycidyl acrylate Download PDFInfo
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- CN101085764A CN101085764A CN 200710025047 CN200710025047A CN101085764A CN 101085764 A CN101085764 A CN 101085764A CN 200710025047 CN200710025047 CN 200710025047 CN 200710025047 A CN200710025047 A CN 200710025047A CN 101085764 A CN101085764 A CN 101085764A
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Abstract
The invention relates to a method for synthesizing a kind of (methyl) acroleic acid glycidic glyceride. It is characterized in that: it takes (methyl) glyceride as raw material, and reacts with epichlorohydrin for ringopening and esterification under catalyst and inhibitor action; then carrying out ring-closure reaction with caustic soda to prepare (methyl) acroleic acid glycidic glyceride. Said catalyst is hexamethylenetetramine or chinoline, 1- methyl glyoxalinyl, and inhibitor is p-hydroxyanisole. The invention is characterized by easy got raw material, low consumption of epichlorohydrin, no utilization of organic disslovant during reaction, short process, simple operation, easy industrialization and little environmental pollution.
Description
One, technical field:
The present invention relates to the synthetic method of a kind of (methyl) glycidyl acrylate, belong to field of chemical technology.
Two, background technology
(methyl) glycidyl acrylate chemistry (methyl) senecioate by name-epoxy propyl ester, structural formula is:
(methyl) glycidyl acrylate is a kind of water white liquid, have two active functional groups, carbon-carbon double bond and epoxy group(ing), be a kind of highly active functional monomer, in the acrylic resin paint of synthetic excellent performance, important purposes is arranged, be widely used in aspects such as fiber process, coating, light-cured resin, tackiness agent, sheet processing, rubber industry.
One-step synthesis is to prepare (methyl) glycidyl acrylate main method at present, and it is a raw material with acrylic or methacrylic acid sodium-salt, epoxy chloropropane, one-step synthesis acrylic or methacrylic acid glycidyl ester; The characteristics of this method are reaction times short (2-4h), productive rate height (generally 92～97%), and good product quality is the method that overseas enterprise generally adopts.But this synthetic method requires whole reaction system anhydrous, and very high to the purity requirement of sodium salt, the sodium salt water content is less than 0.5%, the ester yield is reached more than 92%, and the epoxy chloropropane consumption that exists many (needing excessive 4-10 doubly), and the reactions steps of this method is long, and subsequent disposal is numerous and diverse.
Three, summary of the invention:
At above-mentioned shortcoming, the object of the present invention is to provide that a kind of raw material is easy to get, the epoxy chloropropane consumption is few, in the reaction process without organic solvent, reaction conditions gentleness, easy and simple to handle, safety be easy to the synthetic method of industrialized (methyl) glycidyl acrylate.
Technology contents of the present invention is that the synthetic method of (methyl) glycidyl acrylate is characterized in that: with (methyl) vinylformic acid is raw material, under catalyzer and inhibitor action, carries out the esterification by ring opening reaction with epoxy chloropropane; Carry out ring-closure reaction with sodium hydroxide then and make (methyl) glycidyl acrylate; Catalyzer is hexamethylenetetramine or quinoline, 1-Methylimidazole, and stopper is a MEHQ; Epoxy chloropropane is 1～1.4: 1 (mol) with (methyl) acrylic acid charge ratio in the ring-opening reaction, the ring-opening reaction temperature is 60～100 ℃, the quality consumption of catalyzer is 0.1～1.0% of reactant (methyl) vinylformic acid and an epoxy chloropropane, and the quality consumption of stopper is 0.1～0.3% of reactant (methyl) vinylformic acid and an epoxy chloropropane; The charge ratio 1: 1～1.2 (mol) of epoxy chloropropane and sodium hydroxide in the ring-closure reaction, the ring-closure reaction temperature is 30～50 ℃.
Main reaction formula in the present invention is as follows:
The open loop main reaction:
The closed loop main reaction:
In the formula: R
1=H, CH
3
(methyl) vinylformic acid is methacrylic acid or vinylformic acid in the present invention; (methyl) glycidyl acrylate is glycidyl acrylate or glycidyl methacrylate.
The suitable quality consumption of catalyzer is 0.3～0.7% of reactant (methyl) vinylformic acid and an epoxy chloropropane in invention, and optimum quality consumption is 0.5～0.7% of reactant (methyl) vinylformic acid and an epoxy chloropropane.
Epoxy chloropropane is 1.05～1.3: 1 (mol) with the charge ratio that (methyl) vinylformic acid suits in invention, and optimum charge ratio is 1.1～1.2: 1 (mol); The excessive amount of by-products that can cause too much of epoxy chloropropane increases; It is too high to cross residual at least acid content, and quality product is defective.
The temperature of reaction that ring-opening reaction is suitable among the present invention is 80～100 ℃, and optimum temperature of reaction is 80～90 ℃; Temperature is low excessively, and speed of reaction is low excessively, and temperature is too high, and the formation amount of unwanted polymkeric substance is too much.
The suitable charge ratio of epoxy chloropropane and sodium hydroxide is 1: 1.05～1.1 (mol) among the present invention.
The suitable temperature of reaction of ring-closure reaction is 35～45 ℃ among the present invention; Temperature is low excessively, and speed of response is slow, and temperature is too high, and side reaction is many.
The advantage that the present invention is compared with prior art had is that this method raw material is easy to get, and the epoxy chloropropane consumption significantly reduces, and in the reaction process without organic solvent; The catalyzer that ring-opening reaction adopts is an amines catalyst, belongs to the alkaline organic compound catalyzer, and under this class catalyst action, epoxy chloropropane is active high with (methyl) acrylic acid ring-opening reaction, and reaction conditions relaxes; The present invention also have technical process short, easy and simple to handle, be easy to industrialization, advantage that environmental pollution is little.
Four, specific embodiment
The invention is further illustrated by the following examples, but be not limited to for embodiment.
The raw material epoxy chloropropane that the present invention uses is technical grade, and petrochemical complex limited-liability company in Shandong produces; (methyl) vinylformic acid is technical grade, and Shanghai Ling Feng chemical reagent company limited produces; Sodium hydroxide is technical grade, and Wuhu Ronghui Chemical Co., Ltd. produces; Hexamethylenetetramine and other amine catalyst are analytical pure, and Yixing City Chemical Reagent Plant No.2 produces; MEHQ is a chemical pure, and Chemical Reagent Co., Ltd., Sinopharm Group produces.
The oxirane value of (methyl) glycidyl acrylate detects with hydrochloric acid-acetone method and detects.
Example 1
In the 500mL four-hole boiling flask that has mechanical stirrer, add 117g methacrylic acid (MAA), 1.7g hexamethylenetetramine, 0.4g MEHQ, turn on agitator, be warming up to 80 ℃, drip 175g epoxy chloropropane (ECH), 80～90 ℃ of control reaction temperature, after epoxy chloropropane 6h drips, insulation reaction 1h; Reaction finishes, and reaction product is cooled to below 40 ℃, begins to drip aqueous sodium hydroxide solution 190 grams of 32 weight %, 35～45 ℃ of control reaction temperature, and after 3h drips, insulation reaction 1h; Get glycidyl methacrylate product 129.1g, oxirane value is 0.481eq/100g.
Example 2
In the 500mL four-hole boiling flask that has mechanical stirrer, add the 117g methacrylic acid, 1.7g hexamethylenetetramine, 0.2g MEHQ, turn on agitator, be warming up to 80 ℃, drip 132g epoxy chloropropane (ECH), 60～70 ℃ of control reaction temperature, after epoxy chloropropane 6h drips, insulation reaction 1h; Reaction finishes, and reaction product is cooled to below 40 ℃, begins to drip aqueous sodium hydroxide solution 190 grams of 32 weight %, 35～45 ℃ of control reaction temperature, after 3h drips, insulation reaction 1h, get glycidyl methacrylate product 50.6g, oxirane value is 0.503eq/100g.
Example 3
In the 500mL four-hole boiling flask that has mechanical stirrer, add the 117g methacrylic acid, 1.25g quinoline, 0.4g MEHQ, turn on agitator, be warming up to 80 ℃, drip 155g epoxy chloropropane (ECH), 80～90 ℃ of control reaction temperature, after epoxy chloropropane 5h drips, insulation reaction 1h; Reaction finishes, and reaction product is cooled to below 40 ℃ aqueous sodium hydroxide solution 120 grams of beginning Dropwise 50 weight %, 35～45 ℃ of control reaction temperature, after 3h drips, insulation reaction 2h, get glycidyl methacrylate product 129g, oxirane value is 0.492eq/100g.
Example 4
In the 500mL four-hole boiling flask that has mechanical stirrer, add the 117g methacrylic acid, 1.25g 1-Methylimidazole, 0.4g MEHQ, turn on agitator, be warming up to 80 ℃, drip 155g epoxy chloropropane (ECH), 80～90 ℃ of control reaction temperature, after epoxy chloropropane 5h drips, insulation reaction 1h; Reaction finishes, and reaction product is cooled to below 40 ℃ aqueous sodium hydroxide solution 120 grams of beginning Dropwise 50 weight %, 35～45 ℃ of control reaction temperature, after 3h drips, insulation reaction 1h, get glycidyl methacrylate product 139.6g, oxirane value is 0.449eq/100g.
Example 5
In the 500mL four-hole boiling flask that has mechanical stirrer, add the 117g methacrylic acid, 1.25g hexamethylenetetramine, 0.3g MEHQ, turn on agitator, be warming up to 90 ℃, drip 175g epoxy chloropropane (ECH), 90～100 ℃ of control reaction temperature, after epoxy chloropropane 6h drips, insulation reaction 1h; Reaction finishes, and reaction product is cooled to below 40 ℃, begins to drip aqueous sodium hydroxide solution 190 grams of 32 weight %, 35～45 ℃ of control reaction temperature, after 3h drips, insulation reaction 1h, get glycidyl methacrylate product 118.2g, oxirane value is 0.422eq/100g.
Example 6
In the 500mL four-hole boiling flask that has mechanical stirrer, add the 117g methacrylic acid, 1.25g hexamethylenetetramine, 0.2g MEHQ, turn on agitator, be warming up to 70 ℃, drip 163g epoxy chloropropane (ECH), 70～80 ℃ of control reaction temperature, after epoxy chloropropane 8h drips, insulation reaction 1h; Reaction finishes, and reaction product is cooled to below 40 ℃, begins to drip aqueous sodium hydroxide solution 190 grams of 32 weight %, 35～45 ℃ of control reaction temperature, after 3h drips, insulation reaction 1h, get glycidyl methacrylate product 85g, oxirane value is 0.473eq/100g.
Example 7
In the 500mL four-hole boiling flask that has mechanical stirrer, add 117g methacrylic acid, 2.0g quinoline, 0.4g MEHQ, turn on agitator is warming up to 80 ℃, drips 163g epoxy chloropropane (ECH), 80～90 ℃ of control reaction temperature, after epoxy chloropropane 6h drips, insulation reaction 1h; Reaction finishes, and reaction product is cooled to below 40 ℃, begins to drip aqueous sodium hydroxide solution 190 grams of 32 weight %, 35～45 ℃ of control reaction temperature, after 3h drips, insulation reaction 1h, get glycidyl methacrylate product 121.5g, oxirane value is 0.465eq/100g.
Example 8
In the 500mL four-hole boiling flask that has mechanical stirrer, add 144g vinylformic acid, 2.2g hexamethylenetetramine, 0.4g MEHQ, turn on agitator, be warming up to 80 ℃, drip 222g epoxy chloropropane (ECH), 80～90 ℃ of control reaction temperature, after epoxy chloropropane 6h drips, insulation reaction 1h; Reaction finishes, and reaction product is cooled to below 40 ℃, begins to drip the aqueous sodium hydroxide solution 265g of 32 weight %, 35～45 ℃ of control reaction temperature, after 3h drips, insulation reaction 1h, get glycidyl acrylate product 121g, oxirane value is 0.31eq/100g.
Claims (3)
1, the synthetic method of (methyl) glycidyl acrylate is characterized in that: with (methyl) vinylformic acid is raw material, under catalyzer and inhibitor action, carries out the esterification by ring opening reaction with epoxy chloropropane; Carry out ring-closure reaction with sodium hydroxide then and make (methyl) glycidyl acrylate; Catalyzer is hexamethylenetetramine or quinoline, 1-Methylimidazole, and stopper is a MEHQ; Epoxy chloropropane is 1～1.4: 1 (mol) with (methyl) acrylic acid charge ratio in the ring-opening reaction, the ring-opening reaction temperature is 60～100 ℃, the quality consumption of catalyzer is 0.1～1.0% of reactant (methyl) vinylformic acid and an epoxy chloropropane, and the quality consumption of stopper is 0.1～0.3% of reactant (methyl) vinylformic acid and an epoxy chloropropane; The charge ratio 1: 1～1.2 (mol) of epoxy chloropropane and sodium hydroxide in the ring-closure reaction, the ring-closure reaction temperature is 30～50 ℃.
2, the synthetic method of (methyl) according to claim 1 glycidyl acrylate, it is characterized in that: the quality consumption of catalyzer is 0.3～0.7% of reactant (methyl) vinylformic acid and an epoxy chloropropane, epoxy chloropropane is 1.05～1.3: 1 (mol) with (methyl) acrylic acid charge ratio, and the temperature of reaction of ring-opening reaction is 80～100 ℃; The charge ratio of epoxy chloropropane and sodium hydroxide is 1: 1.05～1.1 (mol), and the suitable temperature of reaction of ring-closure reaction is 35～45 ℃.
3, the synthetic method of (methyl) according to claim 2 glycidyl acrylate, the quality consumption that it is characterized in that catalyzer is 0.5～0.7% of reactant (methyl) vinylformic acid and an epoxy chloropropane, epoxy chloropropane is 1.1～1.2: 1 (mol) with (methyl) acrylic acid charge ratio, and the temperature of reaction of ring-opening reaction is 80～90 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2261220A1 (en) | 2009-06-11 | 2010-12-15 | Hexion Specialty Chemicals Research Belgium S.A. | Process for preparing glycidyl esters of branched monocarboxylic acids |
| CN102464633A (en) * | 2010-11-19 | 2012-05-23 | 曹彩红 | Synthetic method for (methyl) glycidyl acrylate |
| CN102580643A (en) * | 2011-12-30 | 2012-07-18 | 微楷化学（大连）有限公司 | Micro-reaction device and application thereof in synthesis of glycidyl methacrylate |
| CN103614043A (en) * | 2013-11-21 | 2014-03-05 | 天津翔盛粉末涂料有限公司 | Reversible temperature indicating powder coating, and preparation method and application method thereof |
| CN115701284A (en) * | 2020-03-20 | 2023-02-07 | 英格维蒂南卡罗来纳有限责任公司 | Tall oil derived glycidyl ester and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE708463C (en) * | 1938-05-26 | 1941-07-22 | I G Farbenindustrie Akt Ges | Process for the preparation of ª ‡ -carboxylic acid esters of ª † -chloropropylene glycol |
| BE535560A (en) * | 1954-02-11 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2261220A1 (en) | 2009-06-11 | 2010-12-15 | Hexion Specialty Chemicals Research Belgium S.A. | Process for preparing glycidyl esters of branched monocarboxylic acids |
| WO2010142396A1 (en) | 2009-06-11 | 2010-12-16 | Momentive Specialty Chemicals Research Belgium S.A. | Process for preparing glycidyl esters of branched monocarboxylic acids |
| CN102803242A (en) * | 2009-06-11 | 2012-11-28 | 迈图专业化学股份有限公司 | Process for preparing glycidyl esters of branched monocarboxylic acids |
| US8802872B2 (en) | 2009-06-11 | 2014-08-12 | Momentive Specialty Chemicals Inc. | Process for preparing glycidyl esters of branched monocarboxylic acids |
| CN102803242B (en) * | 2009-06-11 | 2015-09-23 | 瀚森公司 | For the preparation of the method for the glycidyl ester of branched monocarboxylic acid |
| CN102464633A (en) * | 2010-11-19 | 2012-05-23 | 曹彩红 | Synthetic method for (methyl) glycidyl acrylate |
| CN102464633B (en) * | 2010-11-19 | 2014-01-01 | 曹彩红 | Synthetic method for (methyl) glycidyl acrylate |
| CN102580643A (en) * | 2011-12-30 | 2012-07-18 | 微楷化学（大连）有限公司 | Micro-reaction device and application thereof in synthesis of glycidyl methacrylate |
| CN103614043A (en) * | 2013-11-21 | 2014-03-05 | 天津翔盛粉末涂料有限公司 | Reversible temperature indicating powder coating, and preparation method and application method thereof |
| CN103614043B (en) * | 2013-11-21 | 2016-02-10 | 天津翔盛粉末涂料有限公司 | A kind of reversible temperature indicating powder coating and preparation method thereof and using method |
| CN115701284A (en) * | 2020-03-20 | 2023-02-07 | 英格维蒂南卡罗来纳有限责任公司 | Tall oil derived glycidyl ester and preparation method thereof |
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| CN100545154C (en) | 2009-09-30 |
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